Foams,compositions,method for making foams and foam covered substrate ii



United States Patent US. Cl. 260-25 20 Claims ABSTRACT OF THE DISCLOSUREThe preparation of foams from (a) organic-liquids having a surfacetension of at least 22.2 dynes per centimeter at 20 C. when in contactwith air and (b) plastisols by the use of a copolymer of SiO, units andunits selected from the group consisting of (CH SiO and Q(CH SiO units,wherein Q is a radical containing a solubilizing group and the ratio ofSiO; units to the total (CH Si and Q(CH Si units is in the range of1:0.6 to 1:12 is disclosed.

This invention relates to foams, compositions for making foams, a methodfor making foams and foam covered substrates.

This application is a continuation of abandoned application Ser. No.430,193, filed Feb. 3, 1965 and entitled Foams, Compositions, Method ForMaking Foams and Foam Covered Substrate, which in turn is acontinuation-in-part of abandoned application Ser. No. 319,512, filedOct. 28, 1963 and entitled Foams and Compositions and Method for MakingFoams.

More particularly this invention relates to composi tions for makingfoams comprising (1) a' material selected from the group consisting of(a) organic liquids having a surface tension of at least 22.2 dynes percentimeter at 20 C. when in contact with air, and (b) plastisols and (2)a copolymer of Si0 units and units selected from the group consisting of(CH SiO and Q(CH SiO units, wherein Q is a radical containing asolubilizing group and the ratio of Si0 units to the total (CH SiandQ(CH Si-units is in the range of 1:0.6 to 1:12, said copolymer beingcompatible with said organic liquid or plastisol and being present in afoam forming amount.

The method of this invention for making the foams comprises expandingthe composition defined above with a gas.

This invention also relates to the foams which are made from thecompositions and by the method set forth above.

This invention further relates to a process of preparing a foam whichcomprises adding to a material selected from the group consisting of (a)organic liquids having a surface tension of at least 22.2 dynes percentimeter at 20 C. when in contact with air, and (b) plastisols, acopolymer of Si0 units and units selected from the group consisting of(CH SiO and Q(CH SiO units, wherein Q is a radical containing asolubilizing group and the ratio of SiO units to the total (CH Si andQ(CH Si units is in the range of 1:0.6 to 1:12 in a foam forming amount,said copolymer being compatible with said organic liquid or plastisoland then expanding said organic liquid or plastisol with a gas.

This invention also relates to an article of manufacture which is asubstrate coated with a cured, open-celled, foam composition comprising(1) a plastisol and (2) a copolymer of SiO- units and units selectedfrom the group consisting 3,5 1 1,788 PatentecLMay 12, 1970 of (CH) SiO,and Q(CH SiO units, wherein Q is a radical containing a solubilizinggroup that makes the copolymer compatible with the plastisol, and theratio of SiO, units to the total (CH Si and Q(CH Si units is in therange of 1:0.6 to 1:12.

The invention still further relates to a substrate, and particularly apaper, coated with about 1 to 10 mils of a cured, open-celled foam. 'Sofar as is known, heretofore no one has been able to apply such a thinlayer of an open-celled foam to paper. A particularly unique, andsometimes very important, characteristic of the foams applied to thesubstrates is that they can be made opencelled at the surface (e.g.porous) as well as being opencelled internally. However, it is alsopossible to make open-celled foams in accordance with this inventionwhich have a surface skin.

The compositions and methods of this invention are useful for preparingfoams which in turn have numerous uses. For example, foams from theorganic liquids are useful as solvent cleaners and applying a thin layerof solvent over a large area. The foam from the plastisols are useful ascushioning and padding in furniture, bedding, transportation seating,etc. Foams from the plastisols can also be used to make gaskets,filters, shock mountings, cleaning sponges, brassiere shapes, toys, wallcoverings, insulation, laminated structures, clothing and apparelpadding, and automotive crash fronts.

The substrates, and particularly paper, coated with the foams of thisinvention find numerous uses. For example, such articles of manufactureare useful as non-slip napkins, bed sheets, cleaning towels and magazinepaper (which can be printed or screened) where an increased bulk butessentially no increase in weight is desired. These articles are alsouseful as filters for cigarettes, automobile air filters,air-conditioning systems (both heating and cooling) in homes andindustry, fuel filters and broadly for almost any gas or liquid. Thecoated substrates can also be used in packaging as a cushioning and/orinsulation material. They can further be used as fabric liners and asfillers between fabrics.

The foam on the substrate can be employed as a carrier for othermaterials such as antiseptics ormedicinals, burn ointments, detergentsand microencapsulated ink whicl'. articles would be useful as bandages,burn dressings cleaning towels or pads, and carbonless carbon paperrespectively. These uses are illustrative of those wherein aropen-celled surface on the foam can be very important or even essential.The term microencapsulated ink is in tended to include a colored ink perse which has been in corporated in or encapsulated by the foam as wella: colorless dyes or chemicals which are developed into i coloredmaterial when brought in contact with the propei reactant. The ink ordye can alternatively be incorporatet or encapsulated prior to itsaddition into the foam if st desired. The latter types of carbonlesscarbon papers without the foam, are known and are described for exam plein US. Pats. 2,548,366; 2,800,457; and 2,800,458.

Other uses of the compositions, foams and coated sub strates of thisinvention will be obvious to those Skillet in the art.

tion with a surface coating as well as surface coatin per se.

h an acidic silica sol. Such a method is fully described US. Pat.2,676,182, the disclosure of said patent being c'rporatedherein 'byreference.

\. particularly useful means for preparing modified coymers containingboth (CH SiO and ts comprises cohydrolyzing a mixture of (CH SiX lH(CHSiX with SiX, and then coupling the desired ibilizing group Q to thecopolymer by reacting the lrogen on the silicon with the unsaturatedgroup of a apound that also contains the desired solubilizing up. Thistype of reaction is well known to those skilled :he art and isillustrated in the examples. The purpose thesolubilizing group in theradical Q is to make the olyrner compatible with organic liquids orplastisols .ch it might not be compatible with otherwise. Any ibilizinggroup can be employed in the copolymers of invention, the particularorganic liquid or plastisol which the copolymer is to be placeddetermining the ice of solubilizing group. Examples of solubilizing upsthat can be employed in the Q radical are the boxyl, ester, amide,amino, mercapto, halohydrocarl, nitrile, nitro, carbonyl and higherhydrocarbon ups.

."he essential characteristics of the copolymer (2) as ned above are thesiloxane units present, the ratio of se siloxane units and thecompatibility of the copolywith the organic liquid or plastisol. Bybeing comible it is meant that the copolymer is at least partially lbleand/or'dispersible in the organic liquid or plasti- The copolymer canalso be completely soluble or dis sible in the organic liquid orplastisol. So far as is wn at this'time, it is believed that when onewants the st stable foam the copolymer is preferably only parly solubleor dispersible rather than completely so. The ipatibility of thecopolymer in a particular system, for mple a plastisol, can becontrolled in several ways. By I of illustration, one can choose aparticular copolymer aim the above definition which has the desireddegree compatibility. Another alternative is to alter the coymer by theQ radical present and thus control the rec of compatibility. Stillanother alternative is to sea plasticizer for use in the plastisol whichgives the red degree of compatibility. Thus it can be seen fromforegoing illustrations that the instant invention has a rimum amount.of flexibility which permits tailoring compositions and products madetherefrom to indiral specifications and needs rather than vice versa. heamount of copolymer used need only be sufficient ause foaming and canvary from one medium to an- :r. The amount will also vary depending onthe parlar application. The copolymer can be used in any :unts from atrace amount to quite large amounts but referably used in an amount from0.1 to 4% by weight at! on the weight of the organic liquid orplastisol. re than 4% can be used but is not preferred for ecoaicreasons.

he copolymer can be used to foam any organic liquid ing a surfacetension of at least 22.2 dynes per centier at 20 C. when in contact withair and with which F compatible. The term organic liquid as used hereinand mixtures of compounds as long as they have the specified surfacetension. Illustrative of the organic liquids that can be foamed areacetic acid, formic acid, n-butyric acid,

, isobutyric acid, oleic acid, o-xylene, benzene, cyclohexane, toluene,methyl benzoate, methyl acetate, ethyl nitrate, ethyl formate, ethylacetate, ethyl acetoacetate, ethyl cinnamate, methyl propionate, methylformate, n-propyl acetate, ethylene glycol, glycerol, benzyl alcohol,ethyl alcohol, n-octyl alcohol, phenol, allyl alcohol, nbutyl alcohol,bromoform, chloroform, bromobenzene, chlorobenzene,.carbontetrachloride, ethylene chloride, methylene chloride, methylene iodide,tetrab romoethane, ethylene oxide, methylethylketone, acetone,benzophenone, quinoline, N-methylanilinc, ethylaniline, dimethylaniline,n-propylamine, benzylamine, pyridine, o-toluidine, triphenyl-phosphine,tristearin, allyl isothiocyanate, diethylcarbonate, ethyl mercaptan,'benzonitrile, nitroethane, nitrobenzene, paraldehyde, benzaldehyde andfurfural.

The plastisols which can be foamed with the copolymer are well-knownmaterials. Plastisols are simply mixtures of a particulate thermoplasticvinyl resin, such as polyvinyl chloride or a resinous copolymer of amajor portion of vinyl chloride and a minor portion of a copolymerizablemonomer such as vinyl acetate, and a high boiling organic liquidplasticizer which is substantially a non-solvent for the particulateresin at ordinary temperatures but is capable of dissolving the resin atelevated temperature to form a single phase material which upon coolingto ordinary temperature is a solid material having good physicalproperties. For more detailed information on plastisols, reference ismade to the article Plastisols and Organosols by E. G. Partridge et al.in Rubber Age, vol. 67, pages 553-560 (August, 1950); the articleCompounding Plastisols for Specific Applications by Clark et al. inRubber Age, vol. 72, pages 343349 (December, 1952); and pages 170-186 ofthe book, The Technology of Solvents and Plasticizers by A. K.Doolittle,published in 1954 by Wiley. This invention is applicable toany of the ordinary plastisols and the term plastisol as used herein isintended to include modified plastisols" i.e., plastisols containing upto 10% by weight of an organic thinner or diluent such as naphtha, thispercentage being based on the sum of the resin and the plasticizer inadmixture therewith. The plastisol will usually consist of theparticulate vinyl resin and from 50 to 150 parts (per parts of resin) ofhigh boiling organic liquid plasticizer, together with small amountsofconventional additives such as stabilizers, pigments, etc. Specificexamples of suitable plasticizers, stabilizers, pigments, etc. aredisclosed in the articles and book referred to above and numerous otherplaces in the literature and hence no useful purpose would be served bylisting them again here.

The particular method by which the organic liquid or plastisolcontaining the copolymer is expanded with a gas will depend on availableequipment and individual preferences. The numerous ways in which gas isincorporated into materials to foam them are well known in the art.These ways include, for example, the chemicals which release a gas underthe desired conditions and called blowing agents in the art; bubbling agas into the material; and mechanically heating air or another gas intothe material. Of course combinations of these methods can also beemployed. I

Any gas can be used to expand the organic liquids or plastisol so longas it produces no undesirable eitects on the resulting or desiredproduct.

In order that those skilled in the art can better understand how thepresent invention can be practiced, the following examples are given byway of illustration and not by way of limitation. a

5 EXAMPLE 1 In four separate bottles 30 g. of isopropyl alcohol, octane,methyl alcohol and nonane were placed. These liquids have surfacetensions of 21.7, 21.8, 22.6 and 22.9 dynes per centimeter respectivelyat 20 C. when in contact with air. To each of these liquids 0.35 g. of acopolymer of Si and (CH SiO in which the ratio of SiO, units to (CH Siunits was in the range of 1:0.6 to 1:1.2 was added. Each of the bottleswas then vigorously shaken. Neither the isopropyl alcohol or octanefoamed whereas both the methyl alcohol and nonane did foam. This exampleshows that organic liquids having surface tensions of less than 22.2dynes per centimeter are not foamed by the copolymer but organic liquidshaving a surface tension of at least 22.2 dynes per centimeter arefoamed by the copolymer.

EXAMPLE 2 .and (CH SiO in which the ratio of Si0 units to (CH Si unitswas in the range of 110.6.to 1:1.2 was added. To the second graduate acopolymer identical to the other was added except that it had beentreated with (CH SiCl. The treatment consisted of adding 1.25% of (CHSiCl to a solution of the copolymer in xylene (60% solids). The mixturewas refluxed for about 4 hours and then cooled. Another 1.25% of (CHSiCl was added to the mixture, then it was refluxed for about 6 hoursand again cooled. The mixture was then heated to reflux again and thenthe xylene was distilled off at 143 C. Finally, 100 cc. of xylene wasadded to the product and the mixture heated to 143 C. to distill off thexylene. There was 0.1% silicone solids added to each of the graduates. Adiffusion stone was placed in the bottom of the graduates and nitrogenbubbled through it at the rate of about 120 ml. per minute. In the firstgraduate, after minutes of bubbling, 39 ml. of the kerosene had beenconverted to foam. The foam had a volume of 424 ml. In the secondgraduate containing the treated copolymer, after 5 minutes of bubbling,56 m1. of the kerosene had been converted to foam. The foam had a volumeof 571 ml.

EXAMPLE 3 A plastisol consisting of 40 g. of a vinyl chloride polymer,40 g. of a polyester plasticizer and 4 g. of a nitrogen producingblowing agent consisting of 70% N,N'-dimethyl-N,N'-dinitrosoterephthalamide and 30% white mineral oil wasprepared. Another plastisol identical to the first was prepared exceptthat it also contained 4 g.

EXAMPLE 4 A one-shot foam was made by first mixing 7.5 g. of refinedtall oil, 2.5 g. of N,N,N',N-tetrakis(2-hydroxypropyl)ethylenediamineand 2.5 g; of trichlorofluoromethane and then adding 7 g. of OCNC H CH CH NCO. The mixture was poured into a bottle and a foam 2% inches inheight obtained. The foam contained numerous open and large cells on thetop and sides. Another oneshot foam identical to the first was preparedexcept that 0.2 g. of a 10% (solids) solution in xylene of a copolymerof SiO- and (CH SiO in which the ratio of SiO units and (CH Si units wasin the range of 1:0.6 to 1:1.2 was also mixed with the first threeingredients prior to the addition of the isocyanate. When this mixturewas poured EXAMPLE 5 A plastisol consisting of 200 g. of dibutylphthalate, 200 g. of a vinyl chloride polymer and 10 g. of a 10%(solids) solution of a copolymer of SiO (CH )3SiO and OH; 92 K 2) (0CHaCHa) l-azhmo H2)s 112 units in which the ratio of SiO units to total(CH Si0 and units was in the range of 1:0.6 to 1:1.2. The copolymer wasprepared by mixing 156.2 g.- (60% solids) of a solution in toluene of acopolymer of SiO;;, (CH SiO and (CH HSiO units in which the ratio of SiOunits to total (CH Si and (CH HSi units was in the range of 1:0.6 to121.2, 176.3 g. of I 237.5 g. of xylene and 0.4 g. of a 1% solution ofplatinum (as chloroplatinic acid) in dimethylphthalate. The mixture wasrefluxed at l32-134 C. forabout 24 hours. The mixture was then cooled,filtered and evaporated to dryness. The product was a soft wax.

A medium fritted glass filter was placed in the bottom of the mixture ofplastisol and this waxy siloxane and air was blown in to make a foam.The foam formed was taken and placed in a 175 C. oven for about 3minutes. The foam had a density of 16 pounds per cubic foot. No foamcould be made from an identical composition that did not contain thecopolymer.

EXAMPLE 6 A plastisol consisting of 50 g. of octyldecyl phthalate. 50 g.of a homopolymer of vinyl chloride having a specific gravity of 1.4, anapparent density of 15 pounds per cubic foot and an average particlesize of 1.7 microns and 2 g. of p,p'-oxybis-(benzenesulfonyl hydrazide),a nitrogentype blowing agent. Another plastisol identical to the firs1one was prepared except that it also contai ned 1 g. of 2 copolymer ofSiO (CH SiO and units in which the ratio of SiO units to the total (CH Sand H(OCH CH O(CH Si(CH units was in th range of 1:0.6 to 1:1.2. Thecopolymer was prepared by mixing 174.4 g. (60% solids) of a solution intoluene o: a copolymer of Slog, (CH SiO and (CH3)2HSiO1/ units in whichthe ratio of SiO units to total (CH S and (CH HSi units was in the rangeof 1:0.6 to 1:1.2 55.3 g. of CH -CHCH O(CH CH O) H,-120.3 g. o: xyleneand 0.3 g. of a 1% solution of platinum (as chloro platinic acid) indimethylphthalate. The mixture was re fluxed at 128-130.2 C. for about24 hours. The mix ture was then cooled, filtered and evaporated todryness The product was a hard wax.

A 3.2 g. sample of the first plastisol mixture was pourer into a can anda 3.0 g. sample of the second mixture whicl contained the copolymer waspoured into an identical can Both cans were placed in a C. oven forabout 1 minutes. The first mixture yielded a foam having a heigh of A ofan inch as compared to the foam from the mix ture containing thecopolymer which had a height of of an inch.

EXAMPLE 7 Two mixtures were prepared. The first mixture con slsted of 10grams of a low molecular weight liquid epox a prepared by the reactionof bisphenol A and epi- )IOhYdl'lfl 1 and 10 dropsof a solution inxylene (50% ds) of a copolymer of and (CH SiO units vhich the ratio ofSiO; units to (CH Si units was in range of 120.6 to 121.2. The secondmixture consisted 10 grams of the same resin and 10 drops of a soluinxylene (50% solids) of a copolymer of S102, i3)3SiO and 0 3): Q somomsio s in which t he ratio of sio units to total (CH Si @omomsuom):

s was in the range of 1:06 to 121.2. This copolyrner prepared asfollows: in a one liter, three-necked fiask ipped with stirrer, plug andDean Stark trap, there was sad 18.5 grams (.15 mol) of vinylcyclohexeneoxide, .8 grams of a copolymer of SiO (CH SiO and :H3)gSiO1/2 units inwhich the ratio of the SiO; units otal (CH Si and 'H(CH Si units was inthe range 6 to 1:12, 52 grams of xylene, 30 ml. of xylene for the nStark trap and 4 drops of a 1.26% solution of inum' (as chloroplatinicacid) in ethanol. The mixture heated for 24 hours at xylene reflux(approximately C.) and then filtered.

ioth of the epoxy resin copolymer mixtures were heat- 0 60 C. and thenfoamed with air from a'fritted-glass dispersion tube. The foam formed inthe first mixture kedow'n to the surface immediately when the air flowstopped whereas the foam formed in the second mix containing themodified copolymer took 60 seconds break down to the surface when theair flow was ped.

EXAMPLE 8 plastisol consisting of 100 g. of a polyvinyl-chloride n, 67g. of dioctyladipate, 33 g. of butylbenzylphthal- 8 g. of an alkylatedpolyaromatic hydrocarbon (the :r three components being plasticizers)and 8 g. of a olyrner of SiO, and (CH3)3SiO1 g units in which the c ofSiO, units to (OHQgSi units was in the range of 6to 1:1.2 was prepared.

he compatibility of the copolymer in the plastisol was :ked by thefollowing procedure. To g. of a mixture :posed of 75% by weight ofdioctyladipate and 25% weight of butylbenzylphthlate there was added 0.8g. L 50% (solids) solution of the copolymer in xylene. 1 resultingsolution or dispersion was cloudy indicating the copolymer was notcompletely soluble in the mm. '5 ml. of xylene was then added to themixture 11 it become clear and then the mixture allowed to 1d overnight.The next day the mixture was cloudy in so one more ml. of xylene wasadded until the mixwas clear again and then the total number of millisof xylene added, 6.0 ml. is the degree of compatity. If the oopolyrnerhad been completely soluble no me (zero ml.) would have been added.

tir was mechanically incorporated into the above plasl by beating it forabout minutes on a Hobart wire p mixer. A stable foam was produced. Thisfoam then knife coated, at room temperature, onto an ab- Jent paper andthen the foam cured in a 177 C. oven about 1 minute. The cured foam wasopen-celled and coating only a few mils thick. The paper thus coatedexcellent for cleaning purposes and had excellent s y- The resin hada-vlscoslty of 11,000-16,000 centipoises, an

ride equivalent weight of 187193, a specific gravity of and a surfacetension of 50 dynes per centimeter.

8 EXAMPLE 9 was foamed by expanding it with air employing a com--mercial Oakes machine. The resulting foam was fused at a temperature ofabout 149 C. The foam had a density of about 11.5 pounds per cubic foot.

EXAMPLE 10 Two plastisols were prepared which consisted of parts of apolyvinylchloride resin, 100 parts of dioctyladipate and 16 parts of a50% (solids) solution of a co- ;polymer of SiO-,; and (CH SiO units inwhich the ratio of S102 units to (CH Si units was in the range of 1:0.6to 1:1.2. The two plastisols differed in that the copolymer used in onehad a degree of compatibility of 0 (i.e. it was completely soluble)while the copolymer used in the other had a degree of compatibility of6.6, both measured by the procedure set forth in Example 8.

Foams were made from both of the above plastisols employing theprocedure of Example 8. The foam from the copolyrner having 0 degree ofcompatibility was less stable and when cured had a density of 47.4pounds per cubic foot whereas the foam from the copolymer having adegree of compatibility of 6.6 was more stable and had a density of 12.8pounds per cubic foot when cured.

EXAMPLE 11 the procedure of Example 8. It had a density of 25.4

pounds per cubic foot.

That which is claimed is:

1. A composition for making foams comprising:

(1) a plastisol which is a mixture of a particulate thermoplastic vinylresin or a resinous copolymcr of a major portion of such a resin and aminor portion of a copolymerizable monomer, and a high boiling organicliquid plasticizer which is substantially a nonsolvent for theparticulate resin at ordinary temperatures but is capable of dissolvingthe resin at elevated temperature to form a single phase material whichupon cooling to ordinary temperature is a solid material, and

(2) at least 0.1% by weight of a copolymer of SiO, units and unitsselected from the group consisting of (CH SiO and Q(CH SiO units,wherein Q is a radical containing a solubilizing group that makes thecopolymer compatible with the material (1) and the ratio of SiO; unitsto the total (CH Si and 1 Q(CH Si units is in the range of 1:0.6 to 1:1.2.

2. The composition of claim 1 wherein the copolymer (2) consistsessentially of SiO, and (CH3)3Sio1 2 units.

3. The composition of claim 1 wherein the copolymer (2) consistsessentially of SiO- (OH SiO and Q( s)2 1/2 units.

4. A process for preparing a foam which comprises adding at least 0.1%byweight of a copolymer consisting essentially of Si0 units and unitsselected from the group consisting of (CH Si0 and Q(CH SiO units,wherein Q is a radical containing a solubilizing group consisting of (CHSiO and Q(CH SiO terial to which it is added, and the ratio of SiO-units to the total (CH 'Si and Q(CH Si units is in the range of 1:0.6 to1:12, to a plastisol which is a mixture of a particulate thermoplasticvinyl resin or a resinous copolymer of a major portion of such a resinand a minor portion of a copolymerizable monomer, and a high boilingorganic liquid plasticizer which is substantially a nonsolvent for theparticulate resin at ordinary temperatures but is capable of dissolvingthe resin at elevated temperature to form a single phase material whichupon cooling to ordinary temperature is a solid material, and thenexpanding said plastisol with a gas.

5. The process of claim 4 wherein the copolymer consists essentially ofSiO: and (CH SiO units.

6. The process of claim 4 wherein the copolymer consists essentially ofSiO;, (CHQgSiO and Q(CH Si units.

7. The process of claim 6 wherein the copolymer consists essentially ofSiO (CH SiO and 8. The process of claim 6 wherein the copolymer consistsessentially of SiO,,, (CH SiO and units.

9. A foam produced by the process of claim 4. 10. A substrate coatedwith a cured, open-celled, foamed composition comprising:

(1) a plastisol which is a mixture of a particulate thermoplastic vinylresin or a resinous copolymer of a major portion of such a resin and aminor portion of a copolymerizable monomer, and a high boiling organicliquid plasticizer which is substantially a non-solvent for theparticulate resin at ordinary temperatures but is capable of dissolvingthe resin at elevated temperature to form a single phase material whichupon cooling to ordinary temperature is a solid material, and (2) atleast 0.1% by weight of a copolymer of 'SiO units and units selectedfrom the group consisting Of (CH3)3SlO1 3 and Q(CH3)3SlO1/2 units,wherein Q is a radical containing a solubilizing group that makes thecopolymer compatible with the material (1) and the ratio of SiO; unitsto the total and Q(CH 'Si units is in .the range of 1:06 to 1:1.2.

11. The article of claim 10 wherein the substrate is paper.

12. The article of claim 11 wherein (2) is a copolymer of SiO, units and(CHQgSiO units.

13. The article of claim 12 wherein the plastisol (1) (1) a plastisolwhich is a mixture of a particulate" thermoplastic vinyl resin or aresinous copolymer of a major portion of sucha resin and a minor portionof a copolymerizable monomer, and a high boiling organic liquidplasticizer which is substantially a non-solvent for the particulateresin at ordinary temperatures but is capable of dissolving the resin atelevated temperature to form a single phase material which upon coolingto ordinary temperature is a solid material, and (2) at least 0.1% byweight of a copolymer of S10 units and units selected from the groupconsisting of (CH3)3SiO and 'Q(CH );SiO units, Q is a radical containinga solubilizing group that makes the copolymer compatible with thematerial (1) and the ratio of SiO: units to the total (CH Si and Q(CH'Si units is in the range of 1:0.6 to 1:1.2. '15. The paper of claim 14wherein (2) was a copo ymer of SiO, units and (CH Si'0 units.

16. The article of claim 11 wherein the foam contains an ink.

17. The article of claim 12 wherein the foam contains an ink.

18. The article of claim 13 wherein the foam contains an ink.

19. The article of claim 14 wherein the foam contains an ink.

20. The article of claim 15 wherein the foam con tains an ink.

References Cited UNITED STATES PATENTS 2,676,182 4/ 1954 Daudt et al.26046.5 3,015,645 1/ 1962 Tyler 260-825 3,041,193 6/1962 Hamway et a1117-l1 3,061,558 10/1962 Alter 2-60-25 3,160,689 12/1964 Brunner260-'2.5 3,271,332 9/1966 Bond et al. 3,298,895 1/ 1967 Plambeck 117-113,338,845 8/1967 Alzner et al. 2602.5

JOHN C. BLEUTGE, Primary Examiner U.S. Cl. X.R.

